EP0406129A1 - Method for the preparation of methylene di(phenylurethane) - Google Patents

Method for the preparation of methylene di(phenylurethane) Download PDF

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Publication number
EP0406129A1
EP0406129A1 EP90420281A EP90420281A EP0406129A1 EP 0406129 A1 EP0406129 A1 EP 0406129A1 EP 90420281 A EP90420281 A EP 90420281A EP 90420281 A EP90420281 A EP 90420281A EP 0406129 A1 EP0406129 A1 EP 0406129A1
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Prior art keywords
bis
carboalkoxyanilino
methane
hydrofluoric acid
rearrangement
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German (de)
French (fr)
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EP0406129B1 (en
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Michel Gubelmann
Christophe Rochin
Christian Allandrieu
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring

Definitions

  • the present invention relates to a process for the preparation of methylenedi (phenylurethane). It relates more particularly to the preparation of methylenedi (phenylurethane) by rearrangement of bis (N-carboalkoxyanilino) methanes.
  • Methylenedi (phenylurethane) commonly known as MDU is a useful intermediate in the manufacture of methylenedi (phenylisocyanate) known by the name MDI. Indeed, the MDU can be pyrolyzed to MDI in a manner known per se. MDI is particularly useful as a raw material for polyurethane foams and elastomers.
  • MDI is conventionally manufactured by phosgenation of diamine which results from the condensation of aniline and formaldehyde.
  • the commercial product is a mixture of the various isomers of MDI and of oligomers commonly designated by poly-methylenedi (phenylisocyanate) PMDI, from which pure MDI can be isolated.
  • Another drawback presented by this type of process lies in the fact that during the condensation step, significant proportions of compounds are formed alongside the desired diphenylmethanedicarbamate.
  • compounds such as N-carboalkoxyanilinophenylmethanes, bis (N-carboalkoxyanilino) methanes, and N, N′-dicarboalkoxyaminobenzylanilines and their derivatives of higher condensation.
  • N, N′-dicarboalcoxyaminobenzylanilines of formula in which R represents an alkyl radical corresponding to the alkyl residue of the alkyl N-phenylcarbamate engaged in the condensation reaction with a methylating agent, (methyleneamino-linked compounds) are not only impurities which are difficult to separate but also difficult to rearrange in the desired product, including in the presence of an alkyl N-phenylcarbamate.
  • the present invention therefore relates to a process for the preparation of methylenedi (phenylurethane) by rearrangement of at least one bis (N-carboalkoxyanilino) methane, if necessary in the presence of at least one alkyl N-phenylcarbarmate, characterized in that that the rearrangement is carried out in the presence of hydrofluoric acid.
  • the bis (N-carboalkoxyanilino) methanes which can be used in the context of the present invention correspond to the formula (I) given above in which R represents an alkyl or cycloalkyl radical containing from 1 to 6 and preferably from 2 to 4 atoms of carbon.
  • the rearrangement in question can be carried out in the presence of an alkyl N-phenylcarbamate in which the alkyl residue contains from 1 to 6 carbon atoms and is advantageously chosen identical to the alkyl radicals of the carboalkoxy groups of the compound of formula (I) implemented.
  • the molar ratio of the latter to bis (carboalkoxyanilino) methane which can vary within wide limits, will advantageously be between 0.5 and 10 and, preferably between 1 and 5.
  • the rearrangement in question is carried out in the presence of hydrofluoric acid and, preferably, in the liquid phase.
  • This acid is preferably anhydrous although a hydrofluoric acid containing water cannot be excluded. Water only slows the reaction. Since the rearrangement in question does not co-produce water, the use of anhydrous hydrofluoric acid will bring an additional advantage, namely, the possibility of easily recycling said acid.
  • hydrofluoric acid The amount of hydrofluoric acid to be used is not critical. Hydrofluoric acid can be used in a large amount relative to the reactants so that it constitutes the solvent in the reaction medium. Hydrofluoric acid may be present in a smaller amount.
  • the molar ratio of hydrofluoric acid to bis (N-carboalkoxyanilino) methane is at least equal to 10 and, preferably, less than or equal to 200. According to an advantageous variant, this ratio will be between 25 and 100.
  • the reaction temperature is generally between - 20 ° and 80 ° C.
  • the temperature will be between 0 and 60 ° C. In fact, beyond 60 ° C, there is both a decrease in the proportion of the 4,4 'isomer of methylenedi (phenylurethane), an increase in derivatives carrying 3 aromatic rings, and an isomerization of the 4 isomer. , 4 ′ in 2,4 ′ isomer.
  • Pressure is not an essential parameter of the process. However, when the reaction temperature exceeds 20 ° C, it is preferable to operate under a pressure higher than atmospheric pressure to maintain the hydrofluoric acid in liquid form.
  • the method according to the invention can be implemented in hydrofluoric acid as solvent or in a mixture of hydrofluoric acid and an organic solvent.
  • organic solvents which can be used in the context of the present process include: aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and halogenated hydrocarbons such as chloroform, methylene chloride, ethylene chloride, chlorocyclohexane, perchlorocyclohexane, chlorobenzene and dichlorobenzene.
  • a solvent represents at most 300% and preferably from 10 to 150% by weight relative to the bis (N-carboalkoxyanilino) methane used.
  • the reaction time can vary within wide limits and is generally between 15 min and 8 hours.
  • the reaction can be carried out batchwise or continuously.
  • the method according to the invention is particularly suitable for rearrangement of bis N- (carboethoxyanilino) methane, if necessary, in the presence of ethyl N-phenylcarbamate.
  • - MDU RR represents the yield of methylene di (ethyl carbanilate) calculated relative to the number of initial moles of groups -CH2-.
  • - 3-Ph represents the yield (RR) of compounds having 3 aromatic rings calculated in an analogous manner
  • - 4.4 ′ represents methylene-4.4 ′ di (ethyl carbanilate) of formula:
  • - 2.4 ′ represents methylene-2,2 ′ di (ethyl carbanilate) .
  • A represents bis (N-carboethoxyanili o methane of formula
  • the mixture is analyzed by gas phase and liquid phase chromatographies.
  • the conversion rate of A is 100% in these examples.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation de méthylènedi(phényluréthane). Elle a plus particulièrement trait à la préparation de méthylènedi(phényluréthane) par réarrangement de bis (N-carboalcoxyanilino) méthanes, le cas échéant en présence d'au moins un N-phénylcarbarmate d'alkyle caractérisé en ce que le réarrangement est réalisé en présence d'acide fluorhydrique.The present invention relates to a process for the preparation of methylenedi (phenylurethane). It relates more particularly to the preparation of methylenedi (phenylurethane) by rearrangement of bis (N-carboalkoxyanilino) methanes, where appropriate in the presence of at least one alkyl N-phenylcarbarmate characterized in that the rearrangement is carried out in the presence hydrofluoric acid.

Description

La présente invention concerne un procédé de préparation de méthylènedi(phényluréthane). Elle a plus particulièrement trait à la préparation de méthylènedi(phényluréthane) par réarrangement de bis (N-carboalcoxyanilino) méthanes.The present invention relates to a process for the preparation of methylenedi (phenylurethane). It relates more particularly to the preparation of methylenedi (phenylurethane) by rearrangement of bis (N-carboalkoxyanilino) methanes.

Le méthylènedi(phényluréthane) couramment appelé MDU est un intermédiaire utile à la fabrication du méthylènedi(phénylisocyanate) connu sous l'appelation MDI. En effet, le MDU peut être pyrolysé en MDI de manière en soi connue. Le MDI est utile notamment en tant que matière première pour les mousses et élastomères de polyuréthanes.Methylenedi (phenylurethane) commonly known as MDU is a useful intermediate in the manufacture of methylenedi (phenylisocyanate) known by the name MDI. Indeed, the MDU can be pyrolyzed to MDI in a manner known per se. MDI is particularly useful as a raw material for polyurethane foams and elastomers.

Le MDI est fabriqué conventionnellement par phosgénation de la diamine qui résulte de la condensation de l'aniline et du formaldéhyde. Le produit commercial est un mélange des divers isomères du MDI et d'oligomères couramment désignés par poly-méthylènedi(phénylisocyanate) PMDI, dont le MDI pur est susceptible d'être isolé.MDI is conventionally manufactured by phosgenation of diamine which results from the condensation of aniline and formaldehyde. The commercial product is a mixture of the various isomers of MDI and of oligomers commonly designated by poly-methylenedi (phenylisocyanate) PMDI, from which pure MDI can be isolated.

Pour des raisons évidentes liées à la toxicité du phosgène et aux inconvénients associés à la génération d'acide chlorhydrique lors de l'étape de phosgénation, de nombreuses recherches ont été entreprises aux fins de proposer des voies d'accès au MDI ne nécessitant pas d'étape de phosgénation.For obvious reasons related to the toxicity of phosgene and the drawbacks associated with the generation of hydrochloric acid during the phosgenation stage, much research has been undertaken in order to propose access routes to MDI which do not require 'phosgenation stage.

C'est ainsi qu'il a été proposé divers procédés de préparation du MDI à partir de N-phénylcarbamates d'alkyle comprenant une première étape de condensation du N-phénylcarbamate avec du formaldéhyde pour former un mélange renfermant du diphénylméthanedicarbamate et des poly-méthylène-­di(phénylcarbamate), homologues supérieurs des méthylènedi(phényl­carbamate) (ou MDU), suivie d'une étape de décomposition thermique.Thus, various methods of preparing MDI from alkyl N-phenylcarbamates have been proposed, comprising a first stage of condensation of N-phenylcarbamate with formaldehyde to form a mixture containing diphenylmethanedicarbamate and poly-methylene. -di (phenylcarbamate), higher counterparts of methylenedi (phenylcarbamate) (or MDU), followed by a thermal decomposition step.

L'un des inconvénients présenté par ce type de procédés réside dans le fait que la proportion de MDI dinucléaires et, en particulier, de l'isomère 4,4′ est insuffisante.One of the drawbacks presented by this type of process lies in the fact that the proportion of dinuclear MDIs and, in particular, of the 4,4 ′ isomer is insufficient.

Un autre inconvénient présenté par ce type de procédés réside dans le fait que lors de l'étape de condensation il se forme aux côtés du diphénylméthanedicarbamate souhaité des proportions notables de composés tels les N-carboalcoxyanilinophénylméthanes, les bis(N-carboalcoxy­anilino)méthanes, et les N,N′-dicarboalcoxyaminobenzylanilines et leurs dérivés de condensation supérieure.Another drawback presented by this type of process lies in the fact that during the condensation step, significant proportions of compounds are formed alongside the desired diphenylmethanedicarbamate. such as N-carboalkoxyanilinophenylmethanes, bis (N-carboalkoxyanilino) methanes, and N, N′-dicarboalkoxyaminobenzylanilines and their derivatives of higher condensation.

Ces diverses impuretés sont gênantes pour la conversion du mélange réactionnel en diisocyanates recherchés.These various impurities are troublesome for the conversion of the reaction mixture into the desired diisocyanates.

Dans le brevet américain n° 4,146,727, il a été proposé de réarranger des impuretés de type N-benzylique de formule (I)

Figure imgb0001
dans laquelle X, Y ou Z peuvent notamment représenter un groupe - NHCOOR, R est un groupe alkyle comportant de 1 à 3 atomes de carbone, leurs dimères, trimères, tétramères, etc, en diphénylméthanedicarbamate par leur mise en contact à une température comprise entre 50 et 170°C, de préférence entre 80 et 130°C avec une quantité catalytique d'un milieu acide protonique fort.In US Patent No. 4,146,727, it has been proposed to rearrange N-benzyl type impurities of formula (I)
Figure imgb0001
 in which X, Y or Z may in particular represent a group - NHCOOR, R is an alkyl group comprising from 1 to 3 carbon atoms, their dimers, trimers, tetramers, etc., in diphenylmethanedicarbamate by bringing them into contact at a temperature between 50 and 170 ° C, preferably between 80 and 130 ° C with a catalytic amount of a strong protonic acid medium.

Il résulte de l'enseignement de ce document qu'essentiellement, seules des impuretés de type N-benzylique seraient formées et valorisables au moins partiellement par le procédé proposé.It follows from the teaching of this document that essentially, only N-benzyl type impurities would be formed and recoverable at least partially by the proposed process.

Dans la demande de brevet français n° 2 460 972 (correspondant au brevet américain n° 4 319 018) il est proposé de réaliser l'étape de condensation du N-phénylcarbamate d'alkyle et du formaldéhyde ou d'une substance générant du formaldéhyde en présence simultanée d'au moins un composé qui peut notamment être choisi parmi les bis(N-carboalcoxyanilino) méthanes et les N,N′-dicarboalcoxyaminobenzylanilines et d'une solution aqueuse acide dont la concentration est ajustée de telle sorte que la cinétique de réaction soit acceptable et que les réactions secondaires soient maintenues à un niveau minimal, à une température comprise entre 10 et 150°C et de préférence entre 20 et 120°C.In French patent application no. 2,460,972 (corresponding to American patent no. 4,319,018) it is proposed to carry out the step of condensing alkyl N-phenylcarbamate and formaldehyde or a substance generating formaldehyde in the simultaneous presence of at least one compound which can in particular be chosen from bis (N-carboalkoxyanilino) methanes and N, N′-dicarboalkoxyaminobenzylanilines and from an acidic aqueous solution the concentration of which is adjusted so that the kinetics of reaction is acceptable and that the side reactions are kept at a minimum level, at a temperature between 10 and 150 ° C and preferably between 20 and 120 ° C.

Le procédé décrit dans cette demande ne permet pas d'éliminer totalement les impuretés en cause.The process described in this application does not allow total elimination of the impurities in question.

La Demanderesse dans le cadre de ses recherches a pu mettre en évidence que les N,N′-dicarboalcoxyaminobenzylanilines de formule

Figure imgb0002
dans laquelle R représente un radical alkyle correspondant au reste alkyle du N-phénylcarbamate d'alkyle engagé dans la réaction de condensation avec un agent méthylénant, (composés à liaison méthylèneamino) sont non seulement des impuretés difficilement séparables mais aussi difficilement réarrangeables en produit recherché, y compris en présence d'un N-phénylcarbamate d'alkyle. La Demanderesse sans vouloir être liée par une explication théorique, est conduite à penser que la formation de ces impuretés indésirables résulterait en quelque sorte du réarrangement d'un bis(N-carboalcoxyanilino) méthane répondant à la formule (I)
Figure imgb0003
 dans laquelle R représente un radical alkyle, dans les conditions jusqu'alors mises en oeuvre lors de l'étape de condensation et/ou de réarrangement.The Applicant in the context of its research has been able to demonstrate that the N, N′-dicarboalcoxyaminobenzylanilines of formula
Figure imgb0002
 in which R represents an alkyl radical corresponding to the alkyl residue of the alkyl N-phenylcarbamate engaged in the condensation reaction with a methylating agent, (methyleneamino-linked compounds) are not only impurities which are difficult to separate but also difficult to rearrange in the desired product, including in the presence of an alkyl N-phenylcarbamate. The Applicant, without wishing to be bound by a theoretical explanation, is led to think that the formation of these undesirable impurities would somehow result from the rearrangement of a bis (N-carboalkoxyanilino) methane corresponding to formula (I)
Figure imgb0003
 in which R represents an alkyl radical, under the conditions previously applied during the condensation and / or rearrangement step.

Il a maintenant été trouvé qu'il est possible de réarranger les bis(N-carboalcoxyanilino) méthanes de formule (I) ci-avant en méthylène di(phényluréthane) avec une sélectivité améliorée et, de procéder audit réarrangement avec une sélectivité remarquable en isomère 4,4′ dudit méthylènedi(phényluréthane).It has now been found that it is possible to rearrange the bis (N-carboalkoxyanilino) methanes of formula (I) above in methylene di (phenylurethane) with improved selectivity and, to carry out said rearrangement with remarkable selectivity in isomer 4.4 ′ of said methylenedi (phenylurethane).

La présente invention a donc pour objet un procédé de préparation de méthylènedi(phényluréthane) par réarrangement d'au moins un bis(N-carboalcoxyanilino) méthane, le cas échéant en présence d'au moins un N-phénylcarbarmate d'alkyle caractérisé en ce que le réarrangement est réalisé en présence d'acide fluorhydrique.The present invention therefore relates to a process for the preparation of methylenedi (phenylurethane) by rearrangement of at least one bis (N-carboalkoxyanilino) methane, if necessary in the presence of at least one alkyl N-phenylcarbarmate, characterized in that that the rearrangement is carried out in the presence of hydrofluoric acid.

Les bis(N-carboalcoxyanilino) méthanes utilisables dans le cadre de la présente invention répondent à la formule (I) donnée ci-avant dans laquelle R représente un radical alkyle, ou cycloalkyle comportant de 1 à 6 et de préférence de 2 à 4 atomes de carbone.The bis (N-carboalkoxyanilino) methanes which can be used in the context of the present invention correspond to the formula (I) given above in which R represents an alkyl or cycloalkyl radical containing from 1 to 6 and preferably from 2 to 4 atoms of carbon.

Ces composés peuvent être produits par réaction de N-phénylcarbamate d'alkyle dans le chlorure de méthylène, servant à la fois de solvant de réaction et d'agent méthylénant en présence de soude à 50 % et d'un agent de tranfert de phase - cf. Annales de Quimica, ser. C, 80, 255 (1984).These compounds can be produced by reaction of alkyl N-phenylcarbamate in methylene chloride, serving both as reaction solvent and as methylating agent in the presence of 50% sodium hydroxide and a phase transfer agent - cf. Annals of Quimica, ser. C, 80 , 255 (1984).

Le réarrangement en cause peut être mis en oeuvre en présence d'un N-phénylcarbamate d'alkyle dont le reste alkyle comporte de 1 à 6 atomes de carbone et est avantageusement choisi identique aux restes alkyles des groupes carboalcoxy du composé de formule (I) mis en oeuvre.The rearrangement in question can be carried out in the presence of an alkyl N-phenylcarbamate in which the alkyl residue contains from 1 to 6 carbon atoms and is advantageously chosen identical to the alkyl radicals of the carboalkoxy groups of the compound of formula (I) implemented.

Lorsqu'un tel carbamate est engagé dans le milieu réactionnel, le rapport molaire de celui-ci au bis(carboalcoxyanilino)méthane, qui peut varier dans de larges limites, sera avantageusement compris entre 0,5 et 10 et, de préférence entre 1 et 5.When such a carbamate is engaged in the reaction medium, the molar ratio of the latter to bis (carboalkoxyanilino) methane, which can vary within wide limits, will advantageously be between 0.5 and 10 and, preferably between 1 and 5.

Le réarrangement en cause est réalisé en présence d'acide fluorhydrique et, de préférence, en phase liquide. Cet acide est de préférence anhydre bien qu'un acide fluorhydrique contenant de l'eau ne soit pas à exclure. L'eau ralentit seulement la réaction. Le réarrangement en cause ne coproduisant pas d'eau, l'utilisation d'acide fluorhydrique anhydre apportera un avantage supplémentaire, à savoir, la possibilité de recycler aisément ledit acide.The rearrangement in question is carried out in the presence of hydrofluoric acid and, preferably, in the liquid phase. This acid is preferably anhydrous although a hydrofluoric acid containing water cannot be excluded. Water only slows the reaction. Since the rearrangement in question does not co-produce water, the use of anhydrous hydrofluoric acid will bring an additional advantage, namely, the possibility of easily recycling said acid.

La quantité d'acide fluorhydrique à mettre en oeuvre n'est pas critique. L'acide fluorhydrique peut être engagé en quantité importante par rapport aux réactifs de telle sorte qu'il constitue le solvant dans le milieu réactionnel. L'acide fluorhydrique peut être présent en quantité plus faible.The amount of hydrofluoric acid to be used is not critical. Hydrofluoric acid can be used in a large amount relative to the reactants so that it constitutes the solvent in the reaction medium. Hydrofluoric acid may be present in a smaller amount.

Pour une bonne mise en oeuvre de l'invention le rapport molaire de l'acide fluorhydrique au bis(N-carboalcoxyanilino) méthane est au moins égal à 10 et, de préférence, inférieur ou égal à 200. Selon une variante avantageuse ce rapport sera compris entre 25 et 100.For a good implementation of the invention the molar ratio of hydrofluoric acid to bis (N-carboalkoxyanilino) methane is at least equal to 10 and, preferably, less than or equal to 200. According to an advantageous variant, this ratio will be between 25 and 100.

La température de réaction est en générale comprise entre - 20° et 80°C.The reaction temperature is generally between - 20 ° and 80 ° C.

Pour une bonne mise en oeuvre du présent procédé la température sera comprise entre 0 et 60°C. En effet, au delà de 60°C on observe à la fois une diminution de la proportion d'isomère 4,4′ du méthylènedi(phényl­uréthane), une augmentation en dérivés porteurs de 3 noyaux aromatiques, et une isomérisation de l'isomère 4,4′ en isomère 2,4′.For a good implementation of the present process, the temperature will be between 0 and 60 ° C. In fact, beyond 60 ° C, there is both a decrease in the proportion of the 4,4 'isomer of methylenedi (phenylurethane), an increase in derivatives carrying 3 aromatic rings, and an isomerization of the 4 isomer. , 4 ′ in 2,4 ′ isomer.

On observe également, en dessous de 60°C, que la proportion de dérivés porteurs de 3 noyaux aromatiques reste faible dans le mélange réactionnel et que plus la température est basse plus la proportion d'isomère 4,4′ recherché est importante dans le méthylènedi(phényluréthane) produit.It is also observed, below 60 ° C., that the proportion of derivatives carrying 3 aromatic rings remains low in the reaction mixture and that the lower the temperature, the higher the proportion of desired 4.4 ′ isomer is found in methylenedi. (phenylurethane) product.

La pression n'est pas un paramètre essentiel du procédé. Toutefois, lorsque la température de réaction dépasse 20°C il est préférable d'opérer sous une pression supérieure à la pression atmosphérique pour maintenir l'acide fluorhydrique sous forme liquide.Pressure is not an essential parameter of the process. However, when the reaction temperature exceeds 20 ° C, it is preferable to operate under a pressure higher than atmospheric pressure to maintain the hydrofluoric acid in liquid form.

Le procédé selon l'invention peut être mis en oeuvre dans l'acide fluorhydrique comme solvant ou dans un mélange d'acide fluorhydrique et d'un solvant organique. A titre d'exemples de solvants organiques utilisables dans le cadre du présent procédé on peut citer : des hydrocarbures aliphatiques tels l'hexane et l'heptane ; des hydrocarbures alicycliques tels le cyclohexane et le méthylcyclohexane ; et les hydrocarbures halogénés tels le chloroforme, le chlorure de méthylène, le chlorure d'éthylène, le chlorocyclohexane, le perchlorocyclohexane, le chlorobenzène et le dichlorobenzène. Quand on utilise un tel solvant, il représente au maximum 300 % et, de préférence, de 10 à 150 % en poids par rapport au bis(N-carboalcoxyanilino)méthane engagé.The method according to the invention can be implemented in hydrofluoric acid as solvent or in a mixture of hydrofluoric acid and an organic solvent. Examples of organic solvents which can be used in the context of the present process include: aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and halogenated hydrocarbons such as chloroform, methylene chloride, ethylene chloride, chlorocyclohexane, perchlorocyclohexane, chlorobenzene and dichlorobenzene. When such a solvent is used, it represents at most 300% and preferably from 10 to 150% by weight relative to the bis (N-carboalkoxyanilino) methane used.

La durée de réaction peut varier dans de larges limites elle est généralement comprise entre 15 mn et 8 heures.The reaction time can vary within wide limits and is generally between 15 min and 8 hours.

La réaction peut être mise en oeuvre en discontinu ou en continu.The reaction can be carried out batchwise or continuously.

En fin de réaction ou du temps imparti à celle-ci on récupère le produit recherché par tous moyens appropriés, par exemple par évaporation de l'acide fluorhydrique.At the end of the reaction or the time allotted to it, we recover the product sought by any appropriate means, for example by evaporation of hydrofluoric acid.

Le procédé selon l'invention convient particulièrement bien au réarrangement du bis N-(carboéthoxyanilino) méthane, le cas échéant, en présence de N-phénylcarbamate d'éthyle.The method according to the invention is particularly suitable for rearrangement of bis N- (carboethoxyanilino) methane, if necessary, in the presence of ethyl N-phenylcarbamate.

Les exemples ci-après illustrent la présente invention.The following examples illustrate the present invention.

Les conventions suivantes y sont utilisées :
- MDU RR(%) : représente le rendement en méthylène di(carbanilate d'éthyle) calculé par rapport au nombre de mole initiales de groupes -CH₂-.
- 3-Ph(%) : représente le rendement (RR) en composés présentant 3 noyaux aromatiques calculé de manière analogue
- 4,4′ : représente le méthylène-4,4′ di(carbanilate d'éthyle) de formule :

Figure imgb0004
- 2,4′ : représente le méthylène-2,2′ di(carbanilate d'éthyle)
. A représente le bis(N-carboéthoxyanili o méthane de formule
Figure imgb0005
 The following conventions are used:
- MDU RR (%): represents the yield of methylene di (ethyl carbanilate) calculated relative to the number of initial moles of groups -CH₂-.
- 3-Ph (%): represents the yield (RR) of compounds having 3 aromatic rings calculated in an analogous manner
- 4.4 ′: represents methylene-4.4 ′ di (ethyl carbanilate) of formula:
Figure imgb0004
 - 2.4 ′: represents methylene-2,2 ′ di (ethyl carbanilate)
. A represents bis (N-carboethoxyanili o methane of formula
Figure imgb0005

EXEMPLE 1 à 3EXAMPLE 1 to 3

Dans un réacteur en Hastelloy de 50 cm3 de capacité, muni d'une agitation magnétique, on charge :
10 mmol de bis(carboéthoxyanilino)méthane (A)
20 g (1 mol) d'acide fluorhydrique anhydre.
Après deux heures de réaction à la température (T) on analyse le mélange par chromatographies en phase gazeuse et en phase liquide.In a Hastelloy reactor with a capacity of 50 cm3, fitted with magnetic stirring, the following are charged:
10 mmol of bis (carboethoxyanilino) methane (A)
20 g (1 mol) anhydrous hydrofluoric acid.
After two hours of reaction at temperature (T), the mixture is analyzed by gas chromatography and in liquid phase.

Les conditions particulières ainsi que les résultats obtenus figurent dans le tableau (I) ci-après :The specific conditions and the results obtained are shown in table (I) below:

Le taux de tranformation de A est de 100 % dans ces exemples : TABLEAU I Ex. N° T °C MDU RR(%) Répartition isomérique (%) 3-Ph (%) - 4,4′ - 2,4′ 1 40 54 94 6 9 2 25 58 93 7 10 3 * 40 91 93 7 3 * dans cet exemple on a ajouté 30 mmol de phénylcarbamate d'éthyle à la charge. The transformation rate of A is 100% in these examples: TABLE I Ex. No. T ° C MDU RR (%) Isomeric distribution (%) 3-Ph (%) - 4.4 ′ - 2.4 ′ 1 40 54 94 6 9 2 25 58 93 7 10 3 * 40 91 93 7 3 * in this example, 30 mmol of ethyl phenylcarbamate was added to the charge.

Dans ces exemples on ne détecte pas la présence de composés à liaison méthylèneamino.In these examples, the presence of methyleneamino-linked compounds is not detected.

EXEMPLES 4 ET 5 :EXAMPLES 4 AND 5:

Dans un réacteur en Hastelloy de 50 cm3 de capacité, muni d'une agitation magnétique, on charge :
30 mmol de phénylcarbamate d'éthyle
10 mmol de bis(carboéthoxyanilino)méthane (A)
x cm3 de dichlorure de méthylène et (20-x)cm3 d'acide fluorhydrique anhydre.In a Hastelloy reactor with a capacity of 50 cm3, fitted with magnetic stirring, the following are charged:
30 mmol of ethyl phenylcarbamate
10 mmol of bis (carboethoxyanilino) methane (A)
x cm3 of methylene dichloride and (20-x) cm3 of anhydrous hydrofluoric acid.

En fin d'essais on analyse le mélange par chromatographies en phase gazeuse et en phase phase liquide.At the end of the tests, the mixture is analyzed by gas phase and liquid phase chromatographies.

Les conditions particulière ainsi que les résultats obtenus en 2 heures de réaction à 40°C sont rassemblés dans le tableau (II) ci-après : TABLEAU II Ex. N° HF cm3 CH₂Cl₂ cm3 MDU RR (%) Répartition isomérique 3-Ph (%) - 4,4′ - 2,4′ 3 20 0 91 93 7 3 4 10 10 ν 100 94 6 1 5 5 15 97 93 7 3 The specific conditions as well as the results obtained in 2 hours of reaction at 40 ° C are collated in table (II) below: TABLE II Ex. No. HF cm3 CH₂Cl₂ cm3 MDU RR (%) Isomeric distribution 3-Ph (%) - 4.4 ′ - 2.4 ′ 3 20 0 91 93 7 3 4 10 10 ν 100 94 6 1 5 5 15 97 93 7 3

Dans ces exemples on ne détecte pas la présence de composés à liaison méthylèneamino.In these examples, the presence of methyleneamino-linked compounds is not detected.

Le taux de transformation de A est de 100 % dans ces exemples.The conversion rate of A is 100% in these examples.

Claims (11)

1° - Procédé de préparation de méthylènedi(phényluréthane) par réarrangement d'au moins un bis(N-carboalcoxyanilino) méthane, le cas échéant en présence d'au moins un N-phénylcarbarmate d'alkyle caractérisé en ce que le réarrangement est réalisé en présence d'acide fluorhydrique.1 ° - Process for the preparation of methylenedi (phenylurethane) by rearrangement of at least one bis (N-carboalkoxyanilino) methane, if necessary in the presence of at least one alkyl N-phenylcarbarmate characterized in that the rearrangement is carried out in the presence of hydrofluoric acid. 2° - Procédé selon la revendication 1, caractérisé en ce que le réarrangement est conduit en phase liquide.2 ° - Method according to claim 1, characterized in that the rearrangement is carried out in the liquid phase. 3° - Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise l'acide fluorhydrique anhydre.3 ° - Process according to claim 1 or 2, characterized in that anhydrous hydrofluoric acid is used. 4° - Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le rapport molaire du N-phénylcarbamate d'alkyle au bis(N-carboalcoxyanilino)méthane est compris entre 0,5 et 10 et, de préférence, entre 1 et 5.4 ° - Process according to any one of the preceding claims, characterized in that the molar ratio of alkyl N-phenylcarbamate to bis (N-carboalkoxyanilino) methane is between 0.5 and 10 and, preferably, between 1 and 5. 5° - Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le bis (N-carboalcoxyanilino)méthane est le bis(N-carboéthoxyanilino)méthane.5 ° - Process according to any one of the preceding claims, characterized in that the bis (N-carboalkoxyanilino) methane is bis (N-carboethoxyanilino) methane. 6° - Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le réarrangement est conduit en présence d'un solvant organique.6 ° - Process according to any one of the preceding claims, characterized in that the rearrangement is carried out in the presence of an organic solvent. 7° - Procédé selon la revendication 6, caractérisé en ce que le solvant organique est le chlorure de méthylène.7 ° - Process according to claim 6, characterized in that the organic solvent is methylene chloride. 8° - Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le rapport molaire de l'acide fluorhydrique au bis(N-carboalcoxyanilino)méthane est supérieur ou égal à 10.8 ° - Process according to any one of the preceding claims, characterized in that the molar ratio of hydrofluoric acid to bis (N-carboalkoxyanilino) methane is greater than or equal to 10. 9° - Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le rapport molaire de l'acide fluorhydrique au bis(N-carboalcoxyanilino)méthane est inférieur ou égal à 200.9 ° - Process according to any one of the preceding claims, characterized in that the molar ratio of hydrofluoric acid to bis (N-carboalkoxyanilino) methane is less than or equal to 200. 10° - Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le rapport molaire de l'acide fluorhydrique au bis(N-carboalcoxyanilino)méthane est compris entre 25 et 100.10 ° - Process according to any one of the preceding claims, characterized in that the molar ratio of hydrofluoric acid to bis (N-carboalkoxyanilino) methane is between 25 and 100. 11° - Procédé selon l'une quelconque des revendications, caractérisé en ce que la température du réarrangement est comprise entre -20° et 80°C et, de préférence, entre 0 et 60°C.11 ° - A method according to any one of claims, characterized in that the rearrangement temperature is between -20 ° and 80 ° C and, preferably, between 0 and 60 ° C.
EP90420281A 1989-06-29 1990-06-13 Method for the preparation of methylene di(phenylurethane) Expired - Lifetime EP0406129B1 (en)

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GB2004866A (en) * 1977-10-03 1979-04-11 Atlantic Richfield Co Process for the preparation of diphenylmethane mono and dicarbamates and polymethylene polyphenyl carbamates by the acid rearrangement of an (alkoxycarbonyl) phenylaminomethyl compound
GB2054584A (en) * 1979-07-09 1981-02-18 Mitsui Toatsu Chemicals Process for producing polymethylene polyphenyl polycarbamates
EP0110732A2 (en) * 1982-12-07 1984-06-13 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing diphenylmethane dicarbamates

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US4146727A (en) * 1977-10-03 1979-03-27 Atlantic Richfield Company Process for the preparation of diphenylmethane mono and dicarbamates and polymethylene polyphenyl carbamates by the acid rearrangement of an (alkoxycarbonyl) phenylaminomethylphenyl compound
DE2904917A1 (en) * 1979-02-09 1980-08-21 Basf Ag METHOD FOR PRODUCING METHYLENE BIS (4-PHENYLCARBAMINE ACID ESTER)
US4230877A (en) * 1979-03-22 1980-10-28 Atlantic Richfield Company Method for increasing the 4,4'dicarbamate isomer of the diphenylmethane dicarbamates during preparation thereof
US4276622A (en) * 1979-07-16 1981-06-30 Crown Controls Corporation Ultrasonic distance measuring circuit
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CA1150293A (en) * 1979-10-01 1983-07-19 Keisuke Wada Process for the production of methylenedicarbanilates
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US4543419A (en) * 1981-02-25 1985-09-24 Atlantic Richfield Company Process for the preparation of diphenylmethane dicarbamates and polymethylene polyphenyl carbamates
DE3202687A1 (en) * 1982-01-28 1983-08-04 Basf Ag, 6700 Ludwigshafen Process for the preparation of methylenebisphenylcarbamic esters and polymethylenepolyphenylcarbamic esters

Patent Citations (3)

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GB2004866A (en) * 1977-10-03 1979-04-11 Atlantic Richfield Co Process for the preparation of diphenylmethane mono and dicarbamates and polymethylene polyphenyl carbamates by the acid rearrangement of an (alkoxycarbonyl) phenylaminomethyl compound
GB2054584A (en) * 1979-07-09 1981-02-18 Mitsui Toatsu Chemicals Process for producing polymethylene polyphenyl polycarbamates
EP0110732A2 (en) * 1982-12-07 1984-06-13 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing diphenylmethane dicarbamates

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DE69014240T2 (en) 1995-05-04
JPH0338560A (en) 1991-02-19
FR2649104A1 (en) 1991-01-04
AR246248A1 (en) 1994-07-29
ES2063946T3 (en) 1995-01-16
BR9003072A (en) 1991-08-27
CA2020099A1 (en) 1990-12-30
KR910000627A (en) 1991-01-29
US5068391A (en) 1991-11-26

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